KR20200080173A - Liquid composition, storage container, porous resin production apparatus, porous resin production method, carrier forming composition, white ink, separation layer forming composition, and reaction layer forming composition - Google Patents

Abstract

A photocurable resin composition capable of forming a porous body and including at least two types of solvents having a specific relationship is disclosed according to the related art. However, such a composition is limited in ingredients that may be used therefor and has a difficulty in designing its ingredients. In addition, it is required that a polymerizable compound and a solvent contained in a liquid composition capable of forming a porous body have high compatibility with each other so that the liquid composition may be spread by various application methods. The present invention provides a liquid composition including a polymerizable compound and a solvent. The liquid composition forms a porous resin and has a light transmission of 30% or more at a wavelength of 550 nm, as determined while agitating the liquid composition, and a device for haze determination obtained by using the liquid composition shows an increase in haze index of 1.0% or more.

Description

Liquid composition, accommodating container, porous resin manufacturing apparatus, porous resin manufacturing method, carrier forming composition, white ink, separation layer forming composition and reaction layer forming composition {LIQUID COMPOSITION, STORAGE CONTAINER, POROUS RESIN PRODUCTION APPARATUS, POROUS RESIN PRODUCTION METHOD, CARRIER FORMING COMPOSITION, WHITE INK, SEPARATION LAYER FORMING COMPOSITION, AND REACTION LAYER FORMING COMPOSITION}

The present invention relates to a liquid composition, a receiving container, a porous resin manufacturing apparatus, a porous resin manufacturing method, a composition for forming a carrier, a white ink, a composition for forming a separation layer, and a composition for forming a reaction layer.

The porous body and the porous membrane can be utilized in various applications such as a separation membrane, an adsorption membrane, and a lead battery separator by utilizing its characteristic functions. Therefore, if there is a liquid composition for forming a porous material that can be easily applied to a multi-purpose handling property, the range of application is greatly expanded.

As a method of forming a porous body, a method of forming a porous body by laminating fine particles has been proposed. This method requires a solution in which fine particles are dispersed, but it is not easy to stably maintain the dispersion state of a solution containing fine particles. In addition, in the case of forming a porous body by lithographic printing, the quality of the product is deteriorated in the long run because the coating device wears out due to fine particles.

Japanese Patent No. 4426157 discloses a photopolymerizable monomer (A), an organic compound (B) that is not compatible with the photopolymerizable monomer (A), and a photopolymerizable monomer (A) and an organic compound (B). A porous forming photocurable resin composition comprising a common solvent (C) and a photopolymerization initiator (D) as essential components is disclosed.

[Patent Document 1] Japanese Patent No. 4426157

However, Japanese Patent No. 4426157 requires the mixing of at least two kinds of solvents in a specific relationship, and thus there is a problem that materials that can be used are limited and material design is difficult. In addition, in order to be a liquid composition for forming a porous resin that can be developed by various application methods, there is a problem that high compatibility is required between the polymerizable compound and the solvent contained in the liquid composition.

The invention according to claim 1 is a liquid composition comprising a polymerizable compound and a solvent, wherein the liquid composition forms a porous resin, and the liquid composition has a light transmittance of 30% or more at a wavelength of 550 nm measured while stirring the liquid composition. , It is a liquid composition having a haze value increase rate of the haze measurement device produced using the liquid composition is 1.0% or more.

The present invention exhibits an excellent effect that a material design is easy and a liquid composition for forming a porous resin having high compatibility between a polymerizable compound and a solvent contained in a liquid composition can be obtained.

1 is a schematic diagram showing an example of a porous resin manufacturing apparatus for realizing the porous resin manufacturing method of the present embodiment.
Fig. 2 is a schematic diagram showing an example of a material injection type molding apparatus.

Hereinafter, embodiments of the present invention will be described.

<< liquid composition >>

The liquid composition of the present embodiment contains a polymerizable compound, a solvent, and other components such as a polymerization initiator as necessary. In addition, the liquid composition is cured to form a porous resin. Therefore, the liquid composition is preferably used as a liquid for forming a porous resin.

In addition, in this embodiment, "liquid composition forms a porous resin" means that the porous resin precursor is formed in the liquid composition as well as when the porous resin is formed in the liquid composition, and the porous resin is used in the next step (for example, a heating process). In addition, it means that the case includes the formation of the porous resin by curing (polymerizing) some components (such as a polymerizable compound) in the liquid composition as well as when the entire liquid composition is cured to form a porous resin. This means that other components (solvents, etc.) are not cured and do not form a porous resin.

<Polymerizable compound>

The polymerizable compound forms a resin by polymerization, and forms a porous resin when polymerized in a liquid composition. The resin formed by the polymerizable compound is preferably a resin having a network structure formed by imparting active energy rays (eg, light irradiation or heating), for example, acrylate resin, methacrylate resin, urethane acrylate Resins, vinyl ester resins, unsaturated polyester resins, epoxy resins, oxetane resins, vinyl ether resins, and resins formed by en-thiol reactions are preferred. In addition, since it is easy to form a structure by using highly reactive radical polymerization, acrylate resins, methacrylate resins, urethane acrylate resins, which are resins formed by polymerizable compounds containing a (meth)acryloyl group, Vinyl ester resin, which is a resin formed by a polymerizable compound containing a vinyl group, is more preferable from the viewpoint of productivity. These may be used individually by 1 type and may use 2 or more types together. When two or more types are used in combination, the combination of the polymerizable compounds is not particularly limited, and may be appropriately selected depending on the purpose. For example, mixing of other resins with a urethane acrylate resin as the main component for flexibility is provided. desirable. In the present invention, a polymerizable compound containing an acryloyl group or a methacryloyl group is used as a polymerizable compound containing a (meth)acryloyl group.

In addition, as the active energy ray, any energy necessary for advancing the polymerization reaction of the polymerizable compound of the liquid composition may be provided, and it is not particularly limited. For example, ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, etc. Can be illustrated. Among these, it is preferable that it is ultraviolet rays. Further, in particular, when a high energy light source is used, the polymerization reaction can proceed without using a polymerization initiator.

It is preferred that the polymerizable compound contains at least one radically polymerizable functional group. Examples thereof include a monofunctional, bifunctional trifunctional or higher radical polymerizable compound, a functional monomer, a radical polymerizable oligomer, and the like. Among these, a radically polymerizable compound having two or more functional groups is preferable.

As a monofunctional radical polymerizable compound, for example, 2-(2-ethoxy ethoxy) ethyl acrylate, methoxy polyethylene glycol monoacrylate, methoxy polyethylene glycol monomethacrylate, phenoxy polyethylene glycol acrylate, 2- Acryloyl oxy ethyl succinate, 2-ethyl hexyl acrylate, 2-hydroxy ethyl acrylate, 2-hydroxy propyl acrylate, tetra hydrofurfuryl acrylate, 2-ethyl hexyl carbitol acrylate, 3-me Methoxy butyl acrylate, benzyl acrylate, cyclo hexyl acrylate, isoamyl acrylate, isobutyl acrylate, methoxy triethylene glycol acrylate, phenoxy tetra ethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, Stearyl acrylate, styrene monomer, and the like. These may be used individually by 1 type and may use 2 or more types together.

As the bifunctional radical polymerizable compound, for example, 1,3-butane diol diacrylate, 1,4-butane diol diacrylate, 1,4-butane diol dimethacrylate, 1,6-hexane diol diacrylate Rate, 1,6-hexane diol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, EO modified bisphenol A diacrylate, EO modified bisphenol F diacrylate, neo Pentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the trifunctional or higher radically polymerizable compound include trimethylol propane triacrylate (TMPTA), trimethylol propane trimethacrylate, EO-modified trimethylol propane triacrylate, PO-modified trimethylol propane triacrylate, and caprolactone modified Trimethylol propane triacrylate, HPA modified trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH modified glycerol triacrylate, EO modified glycerol tri Acrylate, PO-modified glycerol triacrylate, tris(acryloxy ethyl) isocyanurate, dipentaerythritol hexa acrylate (DPHA), caprolactone modified dipenta erythritol hexaacrylate, dipenta erythritol hydroxy penta Acrylate, alkyl modified dipentaerythritol pentaacrylate, alkyl modified dipenta erythritol tetraacrylate, alkyl modified dipenta erythritol triacrylate, dimethylol propane tetraacrylate (DTMPTA), penta erythritol methoxy tetraacrylate , EO-modified phosphoric acid triacrylate, 2,2,5,5-tetra hydroxy methyl cyclopentanone tetra acrylate, and the like. These may be used individually by 1 type and may use 2 or more types together.

The content of the polymerizable compound in the liquid composition is preferably 5.0% by weight or more and 70.0% by weight or less, more preferably 10.0% by weight or more and 50.0% by weight or less, more preferably 20.0% by weight or more and 40.0% by weight or less with respect to the total amount of the liquid composition. desirable. When the content of the polymerizable compound is 70.0% by weight or less, the pore size of the resulting porous body is not excessively small to a few nm or less, so that the porous body has an appropriate porosity, and thus it is possible to suppress the tendency of penetration of liquid and gas to occur. Because it is preferred. In addition, when the content of the polymerizable compound is 5.0% by weight or more, a three-dimensional network structure of the resin is sufficiently formed to obtain a porous structure sufficiently, and the strength of the obtained porous structure tends to be improved, which is preferable.

<solvent>

The solvent (also referred to as “porogen” in the following description) is a liquid compatible with the polymerizable compound, and the solvent is not compatible with the polymer (resin) in the process of polymerizing the polymerizable compound in the liquid composition (phase separation). The polymerizable compound forms a porous resin when polymerized in a liquid composition, and also dissolves a compound (radical polymerization initiator) generating radicals or acids by light or heat. It is preferable that one type of solvent may be used alone, or two or more types may be used in combination, and in the present embodiment, the solvent does not have polymerizability.

The boiling point of one type of porogen alone or when two or more types are used in combination is preferably 50°C or more and 250°C or less at normal pressure, and more preferably 70°C or more and 200°C or less. When the boiling point is 50° C. or higher, vaporization of porogen near room temperature is suppressed, so that handling of the liquid composition is easy and control of the porogen content of the liquid composition is facilitated. In addition, when the boiling point is 250°C or less, the time of the porogen drying process after polymerization is shortened, and the productivity of the porous resin is improved. In addition, since the amount of porogen remaining inside the porous resin can be suppressed, the quality is improved when the porous resin is used as a functional layer such as a material separating layer separating substances or a reaction layer serving as a reaction site.

Moreover, it is preferable that the boiling point of one type of porogen alone or when two or more types are used in combination is 120°C or higher at normal pressure.

Examples of the porogen include ethylene glycols such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, dipropylene glycol monomethyl ether, and esters such as γ-butyrolactone and propylene carbonate. , Amides such as NN dimethyl acetamide, and the like. Further, liquids having a relatively high molecular weight such as methyl tetradecanoate, methyl decanoate, methyl myristate, and tetradecane can also be exemplified. Further, liquids such as acetone, 2-ethyl hexanol and 1-bromo naphthalene can also be exemplified.

In addition, in this embodiment, the liquid illustrated above does not always correspond to porogen. The porogen of the present embodiment is a liquid that is compatible with the polymerizable compound as described above, and is a liquid that is not compatible with the polymer (resin) (which causes phase separation) in the process of polymerizing the polymerizable compound in the liquid composition. That is, whether or not the liquid corresponds to porogen is determined by the relationship between the polymerizable compound and the polymer (resin formed by polymerizing the polymerizable compound).

In addition, since the liquid composition of the present embodiment only needs to contain at least one kind of polymerizable compound and porogen having the above-described specific relationship, the range of material selection in the production of the liquid composition is wide, thereby facilitating the design of the liquid composition. The range of material selection in the production of a liquid composition is broadened, and the corresponding range is widened when there are characteristics required for the liquid composition from a viewpoint other than formation of a porous structure. For example, when discharging a liquid composition by an inkjet method, it is required to be a liquid composition having discharge stability and the like from a viewpoint other than porous formation, but design of the liquid composition is facilitated because the range of material selection is wide.

In addition, since the liquid composition of the present embodiment only needs to contain at least one type of porogen having the above-described specific relationship with the polymerizable compound as described above, the liquid having the above-described specific relationship with the polymerizable compound (not a porogen) Liquid). However, the content of the polymerizable compound and the liquid (which is not a porogen) that does not have the above-mentioned specific relationship is preferably 10.0% by weight or less, more preferably 5.0% by weight or less, and 1.0% by weight relative to the total amount of the liquid composition. It is more preferable that it is the following, and it is especially preferable not to be included.

The content of porogen in the liquid composition is preferably 30.0% by weight or more and 95.0% by weight or less, more preferably 50.0% by weight or more and 90.0% by weight or less, more preferably 60.0% by weight or more and 80.0% by weight or less with respect to the total amount of the liquid composition. Do. When the porogen content is 30.0% by weight or more, the pore size of the obtained porous body is not excessively small to a few nm or less, and thus the porous body has an appropriate porosity, so that the tendency for the penetration of liquid or gas to be difficult to occur can be suppressed. Do. In addition, when the porogen content is 95.0% by weight or less, it is preferable because the three-dimensional network structure of the resin is sufficiently formed to sufficiently obtain the porous structure, and the strength of the obtained porous structure tends to be improved.

The weight ratio of the polymerizable compound content and the porogen content in the liquid composition (polymerizable compound: porogen) is preferably 1.0:0.4 to 1.0:19.0, more preferably 1.0:1.0 to 1.0:9.0, and 1.0:1.5 to 1.0:4.0 is more preferable.

-Polymerization induction phase separation-

In this embodiment, a porous resin is formed by polymerization-induced phase separation. The polymerization-inducing phase separation of the present embodiment shows a state in which the polymerizable compound and the porogen are compatible, but the polymerized product (resin) and the porogen produced during the polymerization of the polymerizable compound are incompatible (which causes phase separation). There are other methods of obtaining a porous body by phase separation, but since a porous body having a network structure can be formed using a polymerization-induced phase separation method, a porous body having high resistance to chemicals and heat can be expected. Other advantages include shorter process times and easier surface modification compared to other methods.

Next, a process of forming a porous resin using polymerization-induced phase separation will be described. The polymerizable compound generates a polymerization reaction by light irradiation or the like to form a resin. During this process, the solubility of the growing resin in the porogen decreases, resulting in phase separation between the resin and the porogen. Finally, the resin forms a porous structure of a network structure having a porous structure filled with pores with porogen or the like. When it is dried, porogen and the like are removed and a porous resin remains. Therefore, in order to form a porous resin having an appropriate porosity, compatibility between a porogen and a polymerizable compound and a resin formed by polymerizing a porogen and a polymerizable compound are considered.

--Hansen solubility parameter (HSP)--

The above compatibility can be predicted through the Hansen solubility parameter (HSP). The Hansen solubility parameter (HSP) is a useful tool for predicting the compatibility of two types of materials, and is a parameter found by Charles M. Hansen. The Hansen solubility parameter (HSP) is expressed by combining the following three parameters (δD, δP and δH) derived experimentally and theoretically. The unit of Hansen solubility parameter (HSP) is ^0.5 MPa or (J/cm ³ ) ^0.5 . (J/cm ³ ) ^0.5 was used in this embodiment.

ΔD: Energy derived from the dispersion power in London.

ΔP: Energy derived from dipole interaction.

ΔH: Energy derived from hydrogen bonding force.

The Hansen solubility parameter (HSP) is a vector quantity expressed as (δD, δP, δH), and is expressed by plotting three parameters in a three-dimensional space (Hansen space) with a sinusoidal axis. Since the Hansen solubility parameter (HSP) of a commonly used substance has a known information source such as a database, it is possible to obtain a Hansen solubility parameter (HSP) of a desired substance by referring to a database, for example. For substances in which the Hansen Solubility Parameter (HSP) is not registered in the database, the Hansen Solubility Parameter (HSP) can be calculated from the chemical structure of the substance or the Hansen Solubility Method described later by using computer program software such as Hansen Solubility Parameters in Practice (HSPiP). Can. The Hansen solubility parameter (HSP) of a mixture containing two or more substances is calculated as the vector sum of the Hansen solubility parameter (HSP) of each substance multiplied by the volume ratio of each substance to the mixture as a whole. In addition, in this embodiment, the Hansen solubility parameter (HSP) of a solvent (porogen) obtained according to a known information source such as a database is referred to as "Hansen solubility parameter of a solvent".

In addition, the relative energy difference (RED) according to the Hansen solubility parameter (HSP) of the solute and the Hansen solubility parameter (HSP) of the solution is expressed by the following equation.

In the above formula, Ra represents the distance between the interactions between the Hansen solubility parameter (HSP) of the solute and the Hansen solubility parameter (HSP) of the solution, and Ro represents the radius of interaction of the solute. The distance (Ra) between interactions between the Hansen solubility parameter (HSP) represents the distance of two types of substances. A smaller value means that two kinds of materials are closer to each other in a three-dimensional space (Hansen space), indicating that the possibility of dissolving (commercially) each other is increased.

Assuming that each Hansen solubility parameter (HSP) for the two types of substances (Solute A and Solution B) is as follows, Ra can be calculated as follows.

HSP ^A = (δD ^A , δP ^A , δH ^A )

HSP ^B = (δD ^B , δP ^B , δH ^B )

Ra = [4×(δD ^A -δD ^B ) ² + (δP ^A -δP ^B ) ² + (δH ^A -δH ^B ) ² ] ^1/2

Ro (the radius of interaction of the solute) can be determined according to, for example, the Hansen dissolution method described below.

--Hansen melting method--

First, a substance for obtaining Ro, and dozens of evaluation solvents (HSP) whose Hansen solubility parameter (HSP) is known (a liquid having a different meaning from the above-mentioned "solvent (porogen)") are prepared, and each evaluation solvent Perform the compatibility test of the target substance for the Hansen solubility parameter (HSP) of the evaluation solvent showing compatibility with the Hansen solubility parameter (HSP) of the evaluation solvent showing no compatibility in the Hansen space. Each is plotted, including the Hansen solubility parameter (HSP) of the evaluation solvent group showing compatibility according to the Hansen solubility parameter (HSP) of each evaluation solvent plotted, but the Hansen solubility parameter of the evaluation solvent group not showing compatibility Create a virtual sphere (Hansen sphere) that does not contain (HSP) in the Hansen space, where the radius of the Hansen sphere becomes the interaction radius R ₀ of the substance, and the center is the Hansen solubility parameter (HSP) of the substance. The evaluator himself sets the evaluation criteria for compatibility between the substance for which the interaction radius R ₀ and the Hansen solubility parameter (HSP) are calculated and the solvent for evaluation where the Hansen solubility parameter (HSP) is known. The evaluation criteria of the embodiment will be described later.

--Interaction radius with Hansen solubility parameter (HSP) of polymerizable compound--

The Hansen solubility parameter (HSP) of the polymerizable compound of the present embodiment and the radius of interaction of the polymerizable compound are determined by the Hansen dissolution method. In addition, the Hansen solubility parameter (HSP) of the polymerizable compound of the present embodiment, obtained according to the following criteria, is determined by the evaluator himself, as the compatibility evaluation standard of the Hansen dissolution method is set as described above. C” and the radius of interaction of the polymerizable compound is represented by “the radius of interaction D of the polymerizable compound”. In other words, "Hansen solubility parameter C of the polymerizable compound" and "Interaction radius D of the polymerizable compound" are commercially established by the evaluator himself, unlike "Hansen solubility parameter of the solvent" obtained according to known information sources such as databases. It is obtained according to the Hansen dissolution method including the sex evaluation criteria.

The Hansen solubility parameter C of the polymerizable compound and the interaction radius D of the polymerizable compound are evaluated for compatibility with a solvent for the evaluation of the polymerizable compound according to [1-1] and [1-2] below (“Polymerized compound and It is calculated|required by evaluation according to "light transmittance of wavelength 550nm of the composition for transmittance measurement measured while stirring the composition for transmittance measurement containing the evaluation solvent).

[1-1] Preparation of composition for measuring transmittance

First, dozens of evaluation solvents for which a polymerizable compound to obtain a Hansen solubility parameter (HSP) and a Hansen solubility parameter (HSP) are known, and a polymerizable compound, a solvent for each evaluation, and a polymerization initiator are as follows. Mixing in proportions to prepare a composition for measuring transmittance. The dozens of evaluation solvents for which the Hansen solubility parameter (HSP) is known use 21 evaluation solvents described below.

-Composition ratio for measuring transmittance-

Polymeric compound to obtain Hansen solubility parameter (HSP): 28.0 wt%

Solvent for evaluation with known Hansen solubility parameter (HSP): 70.0 wt%

Polymerization initiator (Irgacure819, manufactured by BASF): 2.0 wt%

-Evaluation solvent group (21 types)-

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n Tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethyl hexanol, diisobutyl ketone, benzyl alcohol, 1-bromo naphthalene

[1-2] Light transmittance measurement

The prepared transmittance measurement composition is injected into a quartz cell and stirred at 300 rpm using a stirrer while measuring light (visible light) transmittance at a wavelength of 550 nm of the transmittance measurement composition. In this embodiment, when the light transmittance is 30% or more, it is determined that the polymerizable compound and the solvent for evaluation are in a commercial state, and when the light transmittance is less than 30%, the polymerizable compound and the solvent for evaluation are in an incompatible state. In addition, the conditions regarding the measurement of the light transmittance are as follows.

Quartz cell: Special micro cell with screw-over cap (brand name: M25-UV-2)

· Transmittance measurement device: USB4000 manufactured by Ocean Optics

· Stirring speed: 300rpm

Measurement wavelength: 550nm

· Reference: Acquired by measuring the light transmittance of wavelength 550nm while the inside of the quartz cell is air (transmittance: 100%)

In addition, in the present embodiment, an example of the case where the polymerizable compound and the solvent (porogen) contained in the liquid composition (different from the “permeability measurement composition” described above) is “commercially” is as follows. 1-1], the light transmittance is measured using “liquid composition” instead of “composition for measuring transmittance” in [1-2] above. At this time, when the light transmittance is 30% or more, it is determined that the polymerizable compound and the solvent (porogen) contained in the liquid composition are in a "compatibility" state, and when it is less than 30%, a "non-compatibility" state. Further, in the present embodiment, the light transmittance measured using “liquid composition” instead of “the composition for measuring transmittance” in [1-2] above is set to “light transmittance of a wavelength of 550 nm of the liquid composition measured while stirring the liquid composition”. Shows.

--Hansen solubility parameter (HSP) and interaction radius of the resin formed by polymerization of the polymerizable compound--

The Hansen solubility parameter (HSP) of the resin formed by polymerizing the polymerizable compound of the present embodiment and the interaction radius of the resin formed by polymerizing the polymerizable compound are determined by the Hansen dissolution method. In addition, since the evaluation criteria of the compatibility of the Hansen dissolution method as described above are set by the evaluator himself, the Hansen solubility parameter (HSP) of the resin formed by polymerization of the polymerizable compound of the present embodiment obtained according to the following criteria is " Resin Hansen solubility parameter A”, and the interaction radius of the resin formed by polymerization of the polymerizable compound is represented by “resin interaction radius B”. In other words, "Hansen solubility parameter A of resin" and "Radiation radius B of resin" are based on compatibility evaluation criteria set by the evaluator himself, unlike "Hansen solubility parameter of solvent" obtained according to known information sources such as databases. It is obtained according to the containing Hansen dissolution method.

The interaction radius B of the Hansen solubility parameter A of the resin and the resin is evaluated for compatibility with the solvent for evaluating the resin according to the following [2-1, 2-2 and 2-3] (“Polymerized compound and solvent for evaluation). It is calculated|required by the evaluation according to the haze value (turbidity increase rate) of the haze measurement element produced using the composition for haze measurement containing.

[2-1] Preparation of composition for measuring haze

First, dozens of evaluation solvents in which a precursor (polymerizable compound) and a Hansen solubility parameter (HSP) of a resin for which a Hansen solubility parameter (HSP) is to be obtained are prepared, and a polymerizable compound, a solvent for each evaluation, and polymerization The composition for haze measurement is prepared by mixing an initiator in the ratio shown below. The dozens of evaluation solvents for which the Hansen solubility parameter (HSP) is known use 21 evaluation solvents described below.

-Composition ratio for haze measurement-

Precursor (polymerizable compound) of the resin to obtain the Hahnsen solubility parameter (HSP): 28.0 wt%

Solvent for evaluation with known Hansen solubility parameter (HSP): 70.0 wt%

　Polymerization initiator (Irgacure819, manufactured by BASF): 2.0% by weight

-Evaluation solvent group (21 types)-

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl 2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n Tetradecane, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethyl hexanol, diisobutyl ketone, benzyl alcohol, 1-bromo naphthalene

[2-2] Fabrication of haze measurement elements

The resin fine particles are uniformly dispersed on the substrate by spin coating on an alkali-free glass substrate to form a gap. Subsequently, the substrate coated with the gap agent is bonded to each other by facing the alkali-free glass substrate without the gap agent. Next, using the capillary phenomenon, the composition for haze measurement prepared in [2-2] is filled between bonded substrates to produce a “haze measurement device before UV irradiation”. Then, the composition for haze measurement is cured by UV irradiation on the device for haze measurement before UV irradiation. Finally, a “haze measurement element” is manufactured by sealing the periphery of the substrate with a sealing agent. The conditions at the time of production are as follows.

Alkali-free glass substrate: made by Nippon Electric Glass Co., Ltd., 40mm, t = 0.7mm, OA-10G

Gap agent: Sekisui Chemical Co., Ltd. (SEKISUI CHEMICAL CO.,LTD.), resin fine particles micro pearl GS-L100, average particle diameter 100μm

Spin coating condition: 150 μL of dispersion dripping amount, rotation speed of 1000 rpm, rotation time of 30 s

The amount of the composition for measuring haze filled: 160 μL

UV irradiation conditions: UV-LED is used as the light source, light source wavelength 365nm, irradiation intensity 30mW/cm ² , irradiation time 20s

Sealant: TB3035B (Three Bond company)

[2-3] Haze value (turbidity) measurement

The haze value (turbidity) is measured using the haze measurement device and the haze measurement device before UV irradiation. The measured value of the haze measurement element before UV irradiation is referred to (haze value 0), and the rate of increase of the measured value of the haze measurement element (haze value) with respect to the measured value of the haze measurement element before UV irradiation is calculated. The haze value of the haze measurement element is higher as the compatibility between the resin formed by polymerization of the polymerizable compound and the solvent for evaluation is higher, and lower as the compatibility is higher. In the present embodiment, when the haze value increase rate is 1.0% or more, it is determined that the resin and the solvent for evaluation are in a commercial state when the resin and the solvent for evaluation are less than 1.0%. In addition, the apparatus used for measurement is as follows.

Haze measurement device: Haze meter NDH5000 manufactured by Nippon Densoku Industries Co., Ltd., Japan

In addition, in the present embodiment, an example of a case where a polymer (resin) and a solvent (porogen) contained in a liquid composition (distinguishable from the "haze measurement composition" described above) is "not used (which causes phase separation)" Is as follows. First, in [2-2], which is carried out without executing [2-1], a “liquid composition” is used instead of “a composition for measuring haze” to produce a haze measurement device and a haze measurement device before UV irradiation. do. Next, the haze value increase rate is measured using a haze measurement element and a haze measurement element before UV irradiation produced using “liquid composition” in [2-3] above, wherein the haze value increase rate is 1.0% or more. In the case where the polymer (resin) and the solvent (porogen) contained in the liquid composition are judged to be "non-compatibility (causing phase separation)" and less than 1.0%, "compatibility (not causing phase separation)" In addition, in this embodiment, in the [2-2] above, a device for measuring haze manufactured using “liquid composition” instead of “composition for measuring haze” in “2-2] is a haze produced using a “liquid composition”. Measurement element”.

--Relative energy difference (RED) according to Hansen solubility parameter (HSP) of resin and solvent (porogen)--

As described above, Hansen of a resin formed by polymerizing a polymerizable compound determined according to an increase rate of haze value (turbidity) of a haze measuring device produced using a composition for measuring haze containing a polymerizable compound and a solvent for evaluation The relative energy difference (RED) calculated according to the following equation (1) from the solubility parameter A, the interaction radius B of the resin, and the Hansen solubility parameter of porogen is preferably 1.00 or more, more preferably 1.10 or more, and 1.20 The above is more preferable, and 1.30 or more is particularly preferable.

[Equation 1]

When the relative energy difference (RED) according to the Hansen solubility parameter (HSP) of the resin and porogen is 1.00 or more, the resin formed by polymerization of the polymerizable compound in the liquid composition and the porogen easily cause phase separation, thereby forming a porous resin more It is preferable because it becomes easy to become.

--Relative energy difference (RED) according to Hansen solubility parameter (HSP) of the polymerizable compound and the solvent (porogen)--

As described above, the Hansen solubility parameter C of the polymerizable compound determined according to the light transmittance of the wavelength 550 nm of the composition for measuring transmittance measured while stirring the composition for measuring transmittance containing the polymerizable compound and the solvent for evaluation, the corresponding polymerizable compound The relative energy difference (RED) calculated according to Equation 2 below from the interaction radius D of the polymerizable compound determined according to the compatibility of the solvent for evaluation and the Hansen solubility parameter of the solvent is preferably 1.05 or less, and 0.90 or less Is more preferable, more preferably 0.80 or less, and particularly preferably 0.70 or less.

[Equation 2]

When the relative energy difference (RED) according to the Hansen solubility parameter (HSP) of the polymerizable compound and the porogen is 1.05 or less, the polymerizable compound and the porogen tend to show compatibility, and the closer to 0, the more compatible . Therefore, when the relative energy difference (RED) is 1.05 or less, after dissolving the polymerizable compound in porogen, a liquid composition exhibiting high dissolution stability in which the polymerizable compound does not precipitate over time is obtained. Since the polymerizable compound has a high solubility in porogen, it is possible to maintain the ejection stability of the liquid composition, and thus the liquid composition of the present embodiment can be suitably applied to a method of ejecting a liquid composition such as an inkjet method. . In addition, when the relative energy difference (RED) is 1.05 or less, separation between the polymerizable compound and the porogen in the liquid composition state before the polymerization reaction is started is suppressed, thereby preventing the formation of irregular or non-uniform porous resin.

<Polymerization initiator>

The polymerization initiator is a material capable of initiating polymerization of a polymerizable compound by generating active species such as radicals and cations by energy such as light and heat. As a polymerization initiator, a well-known radical polymerization initiator, a cationic polymerization initiator, a base generator, etc. can be used individually by 1 type or in combination of 2 or more types, It is especially preferable to use a photo-radical polymerization initiator.

As the photo-radical polymerization initiator, a photo-radical generator can be used. For example, photo-radical polymerization initiators such as mihira ketone or benzophenone, also known under the trade names Irugacure and Darocure, and more specific compounds include benzophenone, acetophenone derivatives such as α-hydroxy or α-amino acetophenone, 4- Aroyl-1,3-dioxolane, benzyl ketal, 2,2-diethoxy acetophenone, p-dimethyl acetaminophen, p-dimethyl amino propiophenone, benzophenone, 2-chlorobenzophenone, pp'-dichlorobenzo Phenone, pp'-bis diethyl amino benzo phenone, mihira ketone, benzyl, benzoin, benzyl dimethyl ketal, tetra methyl thiuram monosulfide, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, Azobis isobutyronitrile, benzoin peroxide, di-tert-butyl peroxide, 1-hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-one, 1-(4 -Isopropyl phenyl)-2-hydroxy-2-methyl propan-1-one, methyl benzoyl formate, benzoin isopropyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin ether, benzoin isobutyl ether , Benzoin alkyl ethers or esters such as benzoin n-butyl ether and benzoin n-propyl, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethyl amino-1-(4-morpholine phenyl )-Butanone-1,1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(η5-2,4-cyclopentadiene- 1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl) titanium, bis(2,4,6-trimethyl benzoyl)-phenyl phosphine oxide, 2- Methyl-1[4-(methyl thio)phenyl]-2-morpholino propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocure 1173), bis(2 ,6-dimethoxy benzoyl)-2,4,4-trimethyl-pentyl phosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane -1-one mono acyl phosphine oxide, bis acyl phosphine oxide or titanocene, fluoresene, anthraquinone, thioxanthone or chixanthone, furnace Pindimers, trihalomethyl compounds or dihalomethyl compounds, active ester compounds, organic boron compounds, and the like are preferably used.

Further, a photocrosslinking radical generator such as a bisazide compound may be simultaneously contained. In addition, when polymerizing with heat alone, a thermal polymerization initiator such as azobisisobutyronitrile (AIBN), which is a conventional radical generator, can be used.

When the total weight of the polymerizable compound is 100.0 wt% in order to obtain a sufficient curing rate, the content of the polymerization initiator is preferably 0.05 wt% or more and 10.0 wt% or less, and more preferably 0.5 wt% or more and 5.0 wt% or less.

<<Liquid composition manufacturing method>>

The liquid composition is preferably prepared through a process of dissolving a polymerization initiator in a polymerizable compound, a process of further dissolving porogen and other components, and a process of stirring to obtain a uniform solution.

<<Physical properties of liquid composition>>

The viscosity of the liquid composition is preferably 1.0 mPa·s or more and 150.0 mPa·s or less at 25° C. from the viewpoint of workability when applying the liquid composition, more preferably 1.0 mPa·s or more and 30.0 mPa·s or less, and more preferably 1.0 mPa· s or more and 25.0 mPa·s or less are particularly preferable. When the viscosity of the liquid composition is 1.0 mPa·s or more and 30.0 mPa·s or less, even when the liquid composition is applied to an inkjet method, good ejection properties can be provided. Here, the viscosity can be measured using, for example, a viscometer (device name: RE-550L, manufactured by Toki Sangyo Co., Ltd.).

<< porous resin manufacturing apparatus, porous resin manufacturing method >>

1 is a schematic diagram showing an example of a porous resin manufacturing apparatus for realizing the porous resin manufacturing method of the present embodiment.

<Porous resin manufacturing apparatus>

The porous resin manufacturing apparatus 100 is a device for manufacturing a porous resin using the liquid composition. The porous resin manufacturing apparatus 100 includes a printing process part 10 including a process of forming a liquid composition layer by imparting a liquid composition onto the printing substrate 4, and activates a polymerization initiator of the liquid composition layer to activate the polymerizable compound. A polymerization step portion 20 including a polymerization step of obtaining a porous resin precursor 6 by polymerization, and a heating step portion 30 including a heating step of heating the porous resin precursor 6 to obtain a porous resin are provided. . The porous resin manufacturing apparatus 100 includes a transfer section 5 for transferring the printing substrate 4, and the transfer section 5 includes a printing process section 10, a polymerization processing section 20, and a heating processing section 30. In order, the printing substrate 4 is transferred at a preset speed.

-Printing process department-

The printing process part 10 is a printing apparatus 1a which is an example of an imparting means for realizing an imparting step of imparting a liquid composition onto the printing substrate 4, an accommodating container 1b accommodating the liquid composition, and an accommodating container 1b It has a supply tube (1c) for supplying the liquid composition stored in the printing device (1a).

The receiving container 1b accommodates the liquid composition 7, and the printing process unit 10 discharges the liquid composition 7 from the printing apparatus 1a to impart the liquid composition 7 on the printing substrate 4 to provide liquid The composition layer is formed in a thin film form. Further, the container 1b may be configured to be integrated with the porous resin manufacturing apparatus 100, or may be configured to be separated from the porous resin manufacturing apparatus 100. Moreover, the container used for adding to the storage container integrated with the porous resin manufacturing apparatus 100 or the storage container separable from the porous resin manufacturing apparatus 100 may be sufficient.

The printing apparatus 1a is not particularly limited as long as it can impart the liquid composition 7, for example, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating Printing, dip coating, slit coating, capillary coating, spray coating, nozzle coating, gravure printing, screen printing, flexo printing, offset printing, reverse printing, inkjet printing, etc. Any printing device according to the method can be used.

The receiving container 1b and the supply tube 1c can be arbitrarily selected as long as they can stably store and supply the liquid composition 7. It is preferable that the materials constituting the receiving container 1b and the supply tube 1c have light shielding properties in a relatively short wavelength region of ultraviolet light and visible light. This prevents the liquid composition 7 from being polymerized by external light.

-Polymerization process part-

The polymerization process unit 20 circulates a light irradiation device 2a and a polymerization inert gas which are examples of curing means for realizing a curing process for curing a liquid composition by irradiating active energy rays such as heat and light as shown in FIG. A polymerization inert gas circulation device 2b is provided. The light irradiation apparatus 2a obtains a porous resin precursor 6 by photopolymerizing by irradiating light in the presence of a polymerization inert gas to the liquid composition layer formed by the printing process section 10.

The light irradiation device 2a is appropriately selected according to the absorption wavelength of the photopolymerization initiator contained in the liquid composition layer, and is not particularly limited as long as it can initiate and advance the polymerization of the compound in the liquid composition layer, for example, a high pressure mercury lamp , A metal halide lamp, a hot cathode tube, a cold cathode tube, and an ultraviolet light source such as an LED. However, it is preferable to select a light source according to the thickness of the porous film to be formed, because light having a shorter wavelength generally tends to reach the core.

Next, when the irradiation intensity is too strong with respect to the light irradiation intensity of the light irradiation device 2a, the polymerization proceeds rapidly before phase separation occurs sufficiently, so that the porous structure tends to be difficult to obtain. In addition, when the irradiation intensity is too weak, phase separation proceeds to a microscale or higher, and it is easy to cause unevenness and coarsening of the porous body. In addition, the irradiation time also increases, and the productivity tends to decrease. Therefore, the irradiation intensity as is preferred than 10mW / cm ² than 1W / cm ² or less is preferable, and 30mW / cm ² than 300mW / cm ² or less.

Next, the polymerization inert gas circulation device 2b serves to advance the polymerization reaction of the polymerizable compound near the surface of the liquid composition layer by inhibiting the concentration of the polymerized active oxygen contained in the atmosphere. Therefore, the polymerization inert gas used is not particularly limited as long as it satisfies the above function, and examples thereof include nitrogen, carbon dioxide, and argon.

In addition, it is preferable that the O ₂ concentration is less than 20% (environment having a lower oxygen concentration than the atmosphere), more preferably 0% or more and 15% or less, and more preferably 0% or more and 5, considering that the effect of reducing the reduction is effectively obtained. It is more preferable that it is% or less. In addition, the polymerization inert gas circulation device 2b is preferably provided with a temperature control means capable of controlling the temperature in order to realize stable polymerization progress conditions.

-Heating process part-

As shown in FIG. 1, the heating process part 30 is provided with a heating device 3a, and the solvent remaining in the porous resin precursor 6 formed by the polymerization process part 20 is heated by the heating device 3a. And removing the solvent by heating and drying. Thereby, a porous resin can be formed. The heating step 30 may perform a solvent removal step under reduced pressure.

In addition, the heating process unit 30 remains in the polymerization promoting process and the porous resin precursor 6 to further accelerate the polymerization reaction performed in the polymerization process unit 20 by heating the porous resin precursor 6 with a heating device 3a. And an initiator removal step of removing the photopolymerization initiator to be heated and dried by the heating device 3a. In addition, the polymerization promoting process and the initiator removal process may not be performed simultaneously with the solvent removal process, but may be performed before or after the solvent removal process.

In addition, the heating step 30 includes a polymerization completion step of heating the porous body under reduced pressure after the solvent removal step. The heating device 3a is not particularly limited as long as it satisfies the above functions, and examples thereof include an IR heater and a warm air heater.

Further, the heating temperature and time can be appropriately selected depending on the boiling point of the solvent contained in the porous resin precursor 6 or the thickness of the formed film.

-Printing equipment-

As the material of the printing substrate 4, any material can be used regardless of whether it is transparent or opaque. That is, a resin substrate such as a glass substrate or various plastic films, a composite substrate, or the like may be used as the transparent substrate, and various substrates such as a silicon substrate, a metal substrate such as stainless steel, or a laminate thereof may be used as the opaque substrate. Can be used.

Further, the printing substrate 4 may be a recording medium such as plain paper, glossy paper, special paper, or cloth. Moreover, a low-permeability substrate (low-absorption substrate) may be used as the recording medium. The low-permeability substrate means a substrate having a surface having low water permeability, absorbency, or adsorption property, and includes a material that does not open to the outside even though there are a number of voids therein. As the low-permeability substrate, there may be exemplified a recording medium such as paperboard coated with a surface coated with coated paper or waste paper pulp used for commercial printing in an intermediate layer and a back layer.

In addition, as for the shape, any substrate having a curved surface or an uneven shape can be used as long as it is a substrate applicable to the printing process part 10 and the polymerization process part 20.

<< Porous resin >>

The thickness of the porous resin formed by the liquid composition is not particularly limited, but is preferably 0.01 μm or more and 500 μm or less, more preferably 0.01 μm or more and 100 μm or less, and more preferably 1 μm or more and 50 μm or less in consideration of the uniformity of curing during polymerization. It is preferable, and it is particularly preferably 10 μm or more and 20 μm or less. When the thickness is 0.01 μm or more, the surface area of the resulting porous resin becomes large, and the function by the porous resin can be sufficiently obtained. Further, when the thickness is 500 μm or less, it is suppressed that light and heat used during polymerization are non-uniform in the thickness direction, and a uniform porous resin can be obtained in the thickness direction. By producing a uniform porous resin in the thickness direction, it is possible to suppress the structural unevenness of the porous resin and suppress the deterioration of the permeability of liquids and gases. In addition, the thickness of the porous resin is appropriately adjusted according to the application in which the porous resin is used. For example, when using a porous resin as an insulating layer for a power storage element, it is preferable that it is 10 μm or more and 20 μm or less.

The porous resin to be formed is not particularly limited, but a common continuous structure in which a three-dimensional branched network structure of a cured resin is provided as a skeleton, and a number of voids in the porous resin are continuously connected from the viewpoint of ensuring good permeability of liquid and gas ( It is preferred to have a monolithic structure). That is, it is preferable that the porous resin has a plurality of voids, and one void is diffused in three dimensions with communication with other voids around it. By communicating between the pores, the penetration of liquid and gas occurs sufficiently, so that functions such as material separation and reaction field can be efficiently expressed.

Moreover, air permeability is mentioned as one of the properties obtainable by providing a common continuous structure. The air permeability of the porous resin is preferably 500 seconds/100 mL or less, measured in accordance with JIS P8117, and more preferably 300 seconds/100 mL or less. At this time, the air permeability is measured using, for example, a curry type denso meter (manufactured by Toyo Seiki Co., Ltd.).

The cross-sectional shape of the pores provided by the porous resin to be formed may be various shapes such as approximately circular, approximately elliptical, approximately polygonal, and various sizes. Here, it is assumed that the size of the void indicates the length of the longest part of the cross-sectional shape. The size of the void can be obtained from a cross-sectional photograph taken with a scanning electron microscope (SEM). The size of the pores of the porous resin is not particularly limited, but is preferably 0.01 μm or more and 10 μm or less from the viewpoint of permeability of liquids and gases. The porosity of the porous resin is preferably 30% or more, and more preferably 50% or more. The method of making the size and porosity of the pores provided by the porous resin into this range is not particularly limited, for example, the method of adjusting the content of the polymerizable compound in the liquid composition to the above range, the content of porogen in the liquid composition in the above range A method of adjusting and a method of adjusting the irradiation conditions of the active energy ray.

<<Use of porous resin>>

<Use of power storage device or power generation device>

The porous resin formed using the liquid composition of the present embodiment can be used, for example, as an insulating layer for power storage elements or power generation elements. That is, the liquid composition of the present embodiment can be used as a liquid composition for producing an insulating layer of a power storage element or power generation element. When used for such a purpose, it is preferable to form an insulating layer (separator) by, for example, imparting a liquid composition on an active material layer previously formed on the electrode base.

It is known to use, for example, a porous porous insulating layer having a predetermined size of pores or porosity as an insulating layer for power storage elements or power generation elements. On the other hand, when the liquid composition of the present embodiment is used, the porosity or porosity can be appropriately changed by appropriately adjusting the content of the polymerizable compound, the content of porogen, the irradiation conditions of the active energy ray, etc., and the performance aspect of the power storage element and the power generation element. Can improve the degree of freedom of design. In addition, since the liquid composition of the present embodiment can be developed by various application methods, it can be applied by, for example, an inkjet method, so that the degree of freedom in design of the shape surface of the power storage element and the power generation element can be improved.

In addition, the insulating layer is a member that isolates the positive electrode and the negative electrode and also ensures ion conductivity between the positive electrode and the negative electrode. In addition, when represented by an insulating layer herein, it is not limited to the shape of the layer.

In addition, the liquid composition of the present embodiment can be formed on an insulating layer (first insulating layer) for a power storage element or a power generating element to further form an insulating layer (second insulating layer) made of a porous resin layer. By forming the second insulating layer on the first insulating layer, various functions such as heat resistance, impact resistance, and high temperature shrinkage of the entire insulating layer can be added or improved.

The electrode gas is not particularly limited as long as it is a gas having conductivity, and aluminum foil, copper foil, stainless foil, titanium foil, which can be suitably used for secondary batteries, capacitors, especially lithium ion secondary batteries, which are generally power storage devices, are finely etched and etched. Etching foils with holes, through-electrode gases used in lithium ion capacitors, and the like are used. In addition, a carbon-pattern fiber-type electrode used in a power generation device such as a fuel cell may be used as a non-woven fabric or a flat fabric, or one having a fine hole in the through-electrode gas may be used. In addition, in the case of a solar device, a transparent semiconductor thin film such as indium/titanium oxide or zinc oxide on a flat substrate such as glass or plastic may be used in addition to the electrode, or a thin film of a conductive electrode film may be used.

The active material layer is formed by dispersing the active substance or catalyst composition in powder form in a liquid and applying, fixing, and drying the liquid on an electrode gas. Generally, printing using spray, dispenser, die coater or impression coating is used, It is formed by drying after application.

The positive electrode active material is not particularly limited as long as it is a material capable of reversibly occluding and releasing alkali metal ions. In general, an alkali metal-containing transition metal compound can be used as the active material for the positive electrode. For example, as the lithium-containing transition metal compound, a complex oxide containing lithium and at least one element selected from the group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium can be exemplified. For example, lithium-containing transition metal oxides such as lithium cobaltate, lithium nickelate, and lithium manganate, orivine type lithium salts such as LiFePO ₄ , chalcogen compounds such as titanium disulfide, molybdenum disulfide, and manganese dioxide can be exemplified. The lithium-containing transition metal oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal oxide is replaced by a heterogeneous element. As the heterogeneous element, for example, Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B, etc. can be exemplified, especially Mn, Al, Co, Ni And Mg are preferred. The heterogeneous elements may be one kind or two or more kinds. These positive electrode active materials may be used alone or in combination of two or more. Examples of the active material in a nickel hydrogen battery include nickel hydroxide and the like.

The negative electrode active material is not particularly limited as long as it is a material capable of reversibly occluding and releasing alkali metal ions. In general, a carbon material containing graphite having a graphite-type crystal structure can be used as a negative electrode active material. Examples of such a carbon material include natural graphite, spherical or fibrous artificial graphite, poorly graphitizable carbon (hard carbon), bigraphitizable carbon (soft carbon), and the like. Lithium titanate can be exemplified as a material other than the carbon material. In addition, from the viewpoint of increasing the energy density of the lithium ion battery, high-capacity materials such as silicon, tin, silicon alloy, tin alloy, silicon oxide, silicon nitride, and tin oxide can also be preferably used as the negative electrode active material.

Examples of the active material in the nickel-metal hydride battery include a hydrogen storage alloy AB2 or A2B hydrogen storage alloy.

Examples of the positive or negative electrode binder include PVDF, PTFE, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, and polyacrylic acid hexyl Ester, polymethacrylate, polymethyl methacrylate ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinyl pyrrolidone, polyether, polyether sulfone, hexafluoro propylene, Styrene-butadiene rubber, carboxy methyl cellulose, and the like can be used. Also tetrafluoro ethylene, hexafluoro ethylene, hexafluoro propylene, perfluoro alkyl vinyl ether, vinylidene fluoride, chloro trifluoro ethylene, ethylene, propylene, pentafluoro propylene, fluoro methyl vinyl ether, acrylic acid, Copolymers of two or more kinds of materials selected from hexadiene can be used. Moreover, two or more types selected from these can be used in mixture. In addition, the conductive agent included in the electrode is, for example, graphite, which is natural graphite or artificial graphite, carbon black, such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, and conductive fibers, such as carbon fiber or metal fiber, Metal powders such as fluorinated carbon and aluminum, conductive whiskers such as zinc oxide or potassium titanate, and conductive metal oxides such as titanium oxide, organic conductive materials such as phenylene derivatives and graphene derivatives are used.

The active material of a fuel cell is generally used as a catalyst of a cathode electrode and an anode electrode, in which metal fine particles such as platinum, ruthenium or platinum alloy are supported on a catalyst carrier such as carbon. To support the catalyst particles on the surface of the catalyst carrier, for example, the catalyst carrier is suspended in water to form a precursor of the catalyst particles (platinum chloride, dinitro diamino platinum, second platinum chloride, first platinum chloride, bis acetyl acetonate platinum, dichloro Diamine platinum, dichlorotetraamine platinum, second platinum sulfate Ruthenic acid chloride, iridium acid chloride, rhodium acid chloride, ferric chloride, cobalt chloride, chromium chloride, gold chloride, silver nitrate, rhodium nitrate, palladium chloride, nickel nitrate, iron sulfate, And an alloy component such as copper chloride) to dissolve in the suspension, and to form a metal hydroxide by adding alkali to obtain a catalyst carrier supported on the surface of the catalyst carrier. By applying this catalyst carrier to the electrode and reducing it to a hydrogen atmosphere or the like, an electrode coated with catalyst particles (active material) on the surface is obtained.

In the case of a solar cell or the like, the active material may include oxide semiconductor layers such as SnO ₂ , ＺnO, ＺrO ₂ , Nｂ ₂ O ₅ , CeO ₂ , SiO ₂ , and Al ₂ O, in addition to tungsten oxide powder or titanium oxide powder. The pigment is supported, for example, ruthenium-tris-type transition metal complex, ruthenium-bis-type transition metal complex, osmium-tris-type transition metal complex, osmium-bis-type transition metal complex, ruthenium-cis-diaqua- And compounds such as bipyridyl complex, phthalocyanine and porphyrin, and organic-inorganic perovskite crystals.

-Porogen and electrolyte for power storage devices-

When using a porous resin formed of a liquid composition as an insulating layer of a power storage element, it is preferable that the porogen is used as a component included in the electrolytic solution constituting the power storage element. That is, it is preferable that the electrolyte solution is a solution containing porogen and an electrolyte to be described later. In addition to forming the porous resin, a process of removing the porogen by a heating process or the like after forming the porous resin by selecting a preferred porogen as a component included in the electrolyte solution, and a process of separately impregnating the electrolyte with the porous resin, etc. can be omitted. .

When the heating process can be omitted, damage to the porous resin or damage to components other than the porous resin (eg, electrode gas, active material layer, etc.) that may occur due to heating can be suppressed. In particular, by suppressing damage to the porous resin, the short circuit of the power storage element or the reaction error when driving the power storage element can be suppressed, further improving the performance of the power storage element.

Moreover, when performing the process of removing a porogen by a heating process, some porogen may remain in porous. Residual porogen may generate gas due to unexpected side reactions in the power storage element and degrade the performance of the power storage element. Porogens that can also be used as components included in an electrolytic solution (for example, the power storage element may Decreasing the performance can be suppressed by selecting the one that is difficult to reduce the performance, etc.).

As a porogen that is suitably selected when a porous resin is used as an insulating layer of a power storage element, it is preferable to suppress decomposition reaction or gas generation during use of the power storage element (when charging and discharging), for example, propylene carbonate (propylene carbonate) ), ethyl methyl carbonate (ethyl methyl carbonate), dimethyl carbonate (dimethyl carbonate), ethylene carbonate (ethylene carbonate), acetonitrile, γ-butyrolactone, sulfolane, dioxolane, tetrahydrofuran, 2-methyl tetrahydrofuran , Dimethyl sulfoxide, 1,2-dimethoxy ethane, 1,2-ethoxy methoxy ethane, polyethylene glycol, alcohols, and mixtures thereof. Among these, it is preferable to use at least one selected from propylene carbonate (propylene carbonate), ethyl methyl carbonate (ethyl methyl carbonate), dimethyl carbonate (dimethyl carbonate) and ethylene carbonate (ethylene carbonate).

It is preferable that the boiling point of the porogen in which the process to be removed by the heating process or the like after forming the porous resin is omitted is higher than the boiling point of the porogen requiring a process to be removed by the heating process or the like. The high boiling point suppresses the vaporization of the porogen in the manufacturing process and suppresses the change in the composition of the electrolytic solution from the originally anticipated composition. Specifically, it is preferably 80°C or higher, more preferably 85°C or higher, and even more preferably 90°C or higher. In addition, the boiling point of propylene carbonate (propylene carbonate) is 240°C, the boiling point of ethyl methyl carbonate (ethyl methyl carbonate) is 107°C, the boiling point of dimethyl carbonate (dimethyl carbonate) is 90°C, and ethylene carbonate (ethylene carbonate) The boiling point is 244°C.

In addition, when using a porogen that functions as a component included in the electrolytic solution constituting the power storage element as described above, it is preferable that the porous resin manufacturing apparatus 100 of FIG. 1 does not include a heating step 30. .

The electrolyte is a component used when a porous resin formed of a liquid composition as described above is used as an insulating layer for a power storage element. Examples of the electrolyte include solid electrolytes soluble in porogen and liquid electrolytes such as ionic liquids. By incorporating the electrolyte in the liquid composition, the porogen and the electrolyte constituting the remaining components after formation of the porous resin can function as the electrolyte of the power storage element. This can omit the process of removing the porogen by a heating process or the like after forming the porous resin, and separately impregnating the electrolyte with the porous resin.

When the heating process can be omitted, damage to the porous resin, which may be caused by heating, or damage to components other than the porous resin (eg, electrode gas, active material layer, etc.) can be suppressed. In particular, by suppressing damage to the porous resin, a short circuit of the power storage element or a reaction error when driving the power storage element can be suppressed, further improving the performance of the power storage element.

In addition, even if a step of removing the porogen by the heating step is performed, some porogen may remain in the porous body. Residual porogen may generate gas due to unexpected side reactions in the power storage element and degrade the performance of the power storage element. Porogens that can also be used as components included in an electrolytic solution (for example, the power storage element may Decreasing the performance can be suppressed by selecting the one that is difficult to reduce the performance, etc.).

The solid electrolyte is not particularly limited as far as it is soluble in porogen, and for example, inorganic ionic salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, acid-based support salts, and alkali-based support salts may be used. For LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, KCl, NaClO ₃ , NaCl, NaBF4, NaSCN, KBF ₄ , Mg(ClO ₄ ) ₂ , Mg(BF ₄ ) ₂ And the like.

As the liquid electrolyte, various ionic liquids containing a cation component and an anion component can be exemplified. It is preferred that the ionic liquid can maintain a liquid state in a wide temperature range including room temperature.

Examples of the cation component include imidazole derivatives such as N, N-dimethylimidazole salt, N, N-methyl ethyl imidazole salt, and N, N-methyl propyl imidazole salt; Aromatic salts such as pyridinium salt derivatives such as N, N-dimethyl pyridinium salt and N, N-methyl propyl pyridinium salt; And aliphatic quaternary ammonium compounds such as tetraalkyl ammonium salts such as trimethyl propyl ammonium salt, trimethyl hexyl ammonium salt, and triethyl hexyl ammonium salt.

As an anion component, a compound containing fluorine is preferable, for example, in terms of stability in the atmosphere, and ＢＦ _４ ^－ , CＦ ₃ソ_３ ^－ , Ｐ _４ ^－ , （CＦ _３ソ_２ ） _２ Ｎ ^－ , Ｂ (CN _４ ） ^－ Can be illustrated.

The content of the electrolyte is not particularly limited, and may be appropriately selected according to the purpose, but is preferably 0.7 mol/L or more and 4.0 mol/L or less, more preferably 1.0 mol/L or more and 3.0 mol/L or less in the electrolytic solution, and It is more preferable that 1.0 mol/L or more and 2.5 mol/L or less in terms of both the capacity of the device and the output.

<Use of white ink>

Since the liquid composition of the present embodiment is whitened by removing the porogen after forming the porous resin, it can be used, for example, as a white ink applied to a recording medium. In addition, the white ink in the present application is not particularly limited as long as it is an ink capable of forming a white image, and ink other than white (for example, a transparent or non-white color) is also included.

It is generally known that white ink exhibits white color by containing an inorganic pigment such as titanium oxide as a color material. However, since such a white ink has a large specific gravity of a colorant, sediment is easily generated, and there is a problem in that storage stability and discharge stability are poor. In that respect, the white ink of the present embodiment can improve storage stability and discharge stability because it can exhibit white color without containing a colorant such as a pigment or dye as a component other than the liquid composition. Moreover, although the white ink of this embodiment may contain a white color material, it is preferable that it does not contain a white color material substantially. In the case of substantially not containing a white colorant, the content of the white colorant is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, further preferably 0.01% by weight or less, It is even more preferable to be below the detection limit and particularly preferably not contained. In this way, the white ink formed by the white ink can be made lighter because the white ink does not contain a substantially white colorant, and can be preferably used as, for example, white ink for aircraft painting, white ink for automobile painting, and the like.

It is also known that white ink contains several types of polymerizable compounds and these polymers phase-separate and become cloudy when cured. However, such a white ink exhibits a white color by phase separation between polymers, and does not indicate a white color by an air layer, so there is a problem in that the whiteness falls. In this respect, when the liquid composition of the present embodiment is used as a white ink, white color is exhibited by a porous resin having voids as an air layer, and thus high whiteness can be exhibited. In addition, white is a color called "white" as a social notion, and whiteness can be evaluated by measuring brightness (L*) by a spectrophotometer such as X-Rite939, for example, 100% duty or higher. When the surface of the medium is given in a sufficient coating amount, the brightness (L*) and chromaticity (a*, b*) are 70≤L ^* ≤100, -4.5≤a ^* ≤ 2, -6≤b ^* ≤2.5 It is preferable to indicate the range of.

In addition, since the white ink of the present embodiment forms a layer made of a porous resin when applied to a recording medium, a base layer (primer layer) that improves the fixability of other inks (such as ink containing a color material) applied thereafter. It may be used as a primer ink for producing.

In general, when a low-permeable substrate or a non-permeable substrate such as a coating paper, a glass substrate, a resin film substrate, or a metal substrate is used as a recording medium, there is a problem that the fixing property of the ink with respect to the substrate decreases. In this respect, when the white ink (primer ink) of the present embodiment is used, the white ink (primer ink) has high fixability to a low-permeability substrate or a non-permeable substrate, and thus, the fixability of other inks later applied on the base layer Improve it. In addition, even if another ink (such as an ink containing a colorant) to be applied later is a permeable ink (aqueous ink, etc.) that is difficult to use for a low-permeability substrate or a non-permeable substrate, the colorant is penetrated and diffused into the porous resin surface while the ink component penetrates and diffuses. Can settle.

In addition, since the white ink (primer ink) forms a white receiving layer, the color and transparency of the recording medium can be concealed to improve the image density of other inks (such as ink containing a colorant) which are later applied.

<Use for solid modeling>

Since the liquid composition of the present embodiment can form a porous resin layer having a layer thickness in the height direction, a plurality of layers of the porous resin layer can be stacked to form a three-dimensional object. That is, the liquid composition of this embodiment can be used as a composition for three-dimensional shaping to mold a three-dimensional object. In general, in three-dimensional molding, distortion of the three-dimensional molding due to curing shrinkage exists as a problem. In this regard, since the composition for three-dimensional molding containing the liquid composition of the present embodiment forms a porous body having a network structure according to the polymerization-inducing phase separation, the internal stress during polymerization is relaxed by the network structure, resulting in curing shrinkage. The distortion of the sculpture to be said is suppressed.

Next, a molding apparatus and a molding method for molding a three-dimensional object will be described with reference to FIG. 2. 2 is a schematic view showing an example of a molding apparatus of a material injection method. The molding apparatus of FIG. 2 includes discharge means for discharging a liquid composition by an inkjet method or the like (an example of a dispensing means) and curing means for irradiating the discharged liquid composition with active energy rays to cure, and discharge and discharge by the discharge means. It is a device to mold a three-dimensional object by sequentially repeating curing by the curing means. In addition, the molding method realized by the molding apparatus of FIG. 2 includes a discharging process (an example of a discharging process) for discharging a liquid composition by an inkjet method and a curing process for irradiating and curing active energy rays to the discharged liquid composition. This is a method of molding a three-dimensional object by sequentially repeating the discharge process and the curing process.

The molding apparatus and molding method will be described in detail. The molding apparatus 39 of FIG. 2 discharges the composition for the first three-dimensional molding from the discharge head unit 30 for moldings using a head unit (moving in the AB direction) in which an inkjet head is arranged, and a discharge head unit 31 for a support , 32) discharging the composition for the second steric molding having a different composition from the composition for the first steric molding, and laminating while curing the composition for each steric molding by means of adjacent ultraviolet irradiation means 33 and 34. More specifically, for example, the composition for the second solid molding is ejected from the ejection head units 31 and 32 for support on the molding support substrate 37 and irradiated with an active energy ray to cure to form a first support layer having a stacked portion. After that, the process of forming the first structured layer by discharging the composition for the first three-dimensional molding from the discharge head unit 30 for molding and irradiating and curing the active energy ray to form the first structured layer can be moved in the vertical direction according to the number of stacking. By repeating several times while lowering the stage 38, the support layer and the molding layer are stacked to produce a three-dimensional molding 35. Thereafter, the support stack portion 36 is removed as necessary. In addition, although only one discharge head unit 30 for moldings is provided in FIG. 2, two or more discharge head units 30 may be provided.

<Use of laminates>

The liquid composition of the present embodiment is applied to various objects such as a substrate and cured, so that a porous resin layer can be laminated to various objects such as a substrate. That is, the liquid composition of the present embodiment can be used as a composition for forming a laminate to form a laminate having an object, such as a substrate, and a porous resin layer formed on the object. Specifically, as described above, a liquid composition used for a power storage element or a power generation element, a liquid composition used for a white ink, and a liquid composition used for three-dimensional molding can be exemplified. The liquid composition used for the power storage element or the power generation element is applied to the active material layer to laminate a porous resin layer serving as an insulating layer, and the liquid composition used for white ink is applied to a recording medium to form a porous resin layer resulting in a white image. The lamination, and the liquid composition used for the three-dimensional shaping is applied to the porous resin layer after the curing process, thereby laminating the porous resin layer which is a defined layer of the three-dimensional molding. In general, when a layer is stacked on an object, such as a substrate, when the adhesive force at the interface is weak, the separation between the object and the layer is likely to occur because the interface exists between the object and the layer. In particular, when layer formation is layered by a polymerization reaction, distortion tends to occur in the polymer during polymerization, and it is likely to cause peeling of the object and the layer. In this regard, when the liquid composition of the present embodiment is used as a laminate, a porous body having a network structure is formed according to separation of the polymerization-inducing phase. It is preferable because distortion of the formed object is suppressed and, as a result, peeling of the object and the layer is suppressed.

<Use of carrier>

When the porous composition is formed by mixing the liquid composition of the present embodiment with a functional material, a support material having a functional material supported on the surface of the porous resin can be prepared. That is, the composition containing the liquid composition and the functional material of the present embodiment can be used as a composition for forming a support body for preparing a support body carrying a functional material. Here, the surface of the porous resin is meant to include not only the outer surface of the porous resin, but also an inner surface communicating with the outside. Since the functional material can be supported in the pores communicating with the outside, the surface area capable of supporting the functional material increases.

When the composition for forming a carrier of the present embodiment is used, the porosity and porosity can be changed by appropriately adjusting the content of the polymerizable compound, the content of porogen, the irradiation conditions of the active energy ray, etc., and the design freedom of the performance surface of the carrier is improved. I can do it. In addition, since the composition for forming a support member of the present embodiment can be developed by various application methods, it can be applied by, for example, an inkjet method, so that the design freedom of the shape surface of the support member can be improved. Specifically, the carrier can be uniformly formed not only on the flat surface but also on the curved surface, and the effort of adjusting the shape by cutting the carrier according to the shape of the object can be omitted. In addition, a droplet may be formed by ejecting by an inkjet method, and an active energy ray may be irradiated to an emergency droplet or a separate droplet attached to a substrate to form a carrier having a particle shape.

The functional material is a material that exerts a predetermined function directly or indirectly, and is preferably a material that increases or improves its function according to an increase in the area supported on the porous resin, and the supported functional material is external and/or external It is more preferable that the substance exhibiting the corresponding function by being located on the inner surface communicating with each other (that is, the substance exhibiting the function suppressed when located on the inner surface not communicating with the outside). Further, the functional substance may be a substance that dissolves in a liquid composition or a substance that disperses, but is preferably a substance that disperses. Examples of the functional material are not particularly limited, and examples thereof include a photocatalyst and a bioactive material.

A photocatalyst is a material that exhibits photocatalytic activity when light in a specific wavelength region (excitation light having energy above a band gap between a valence band and a conduction band of the photocatalyst) is irradiated. The photocatalyst exhibits a photocatalytic activity, and can exhibit various effects such as antibacterial action, deodorization and deodorization action, and decomposition of harmful substances such as volatile organic compounds (VOC).

Examples of the photocatalyst include anatase-type or rutile-type titanium oxide (IＶ) (TIOO ₂ ), tungsten oxide (II) (Ｗ ₂ O ₃ ), tungsten oxide (IＶ) (ＷO ₂ ), tungsten oxide (ＶI) (ＷO ₃ ) ), zinc oxide (ＺnO), iron oxide (II) (Ｆe ₂ O ₃ ), strontium titanate (SrTIOO ₃ ), bismuth oxide (II) (ＢI _{2 2} O ₃ ), bismuth vanadate (ＢIＶO ₄ ), tin oxide ( II) (SnO), tin oxide (IＶ) (SnO ₂ ), tin oxide (ＶI) (SnO ₃ ), zirconium oxide (ＺrO ₂ ), cerium oxide (II) (CeO), cerium oxide (IＶ) (CeO ₂ ), barium titanate (ＢaTio ₃ ), indium oxide (III) (In ₂ O ₃ ), copper oxide (I) (Cu ₂ O), copper oxide (II) (CuO), potassium tantalate (ＫTaO ₃ ), niobium Metal oxides such as potassium acid (ＫNHO ₃ ); Metal sulfides such as cadmium sulfide (CdS), zinc sulfide (Ｚns), and indium sulfide (Ins); Metal selenides such as cadmium selenide (CdSEO ₄ ) and zinc selenide (ＺNSe); Metal nitrides, such as gallium nitride (GaAN), etc. can be illustrated, but titanium oxide (IＶ) (TiO ₂ ), tin oxide (IＶ) (SnO ₂ ), tungsten oxide (II) (Ｗ ₂ O ₃ ), tungsten oxide ( It is preferable to contain at least one kind selected from (IＶ) (ＷO ₂ ) and tungsten oxide (ＶI) (ＷO ₃ ), and it is more preferable to include anatase-type titanium oxide (IＶ) (TiO ₂ ).

The bioactive substance is an active ingredient used to exert a physiological effect on a living body. For example, in addition to low molecular compounds including pharmaceutical compounds, food compounds, cosmetic compounds, etc., biopolymers such as proteins such as antibodies, enzymes, nucleic acids such as DNA, RNA, etc. And polymer compounds containing the same. In addition, the "physiological effect" is an effect that occurs when a bioactive substance exerts physiological activity at a target site, for example, it affects quantitative and/or qualitative changes and effects on a living body, tissue, cell, protein, DNA, and RNA. "Physiological activity" means that a physiologically active substance changes and affects a target site (eg, target tissue, etc.). The target site is preferably a cell surface or a receptor present in the cell, for example. In this case, a signal is transmitted to the cell by the physiological activity that the physiologically active substance binds to a specific receptor, resulting in a physiological effect. The bioactive substance may be a substance that, after being converted into a mature form by an enzyme in vivo, binds to a specific receptor and exerts a physiological effect. In this case, it is assumed herein that the substance before conversion to the mature form is also included in the bioactive substance. Further, the bioactive substance may be a substance produced by an organism (human or non-human organism), or may be an artificially synthesized substance. When a particulate carrier is formed using a liquid composition containing such a physiologically active substance, it is used in a particle that delivers the physiologically active substance to a target site in order to exert a desired physiological effect, that is, used in a drug delivery system (DDS) It can be used as a sustained-release particle that continuously releases a drug or a long-term particle. In addition, when a sheet-like carrier is formed using a liquid composition containing a bioactive substance, it can be used as a sustained release sheet that continuously releases the drug in the long term.

<Use of surface modification>

The outer surface of the porous resin formed by the liquid composition of the present embodiment is formed with fine irregularities derived from the porous material, and accordingly, the wettability can be controlled. Specifically, when the resin constituting the porous resin is hydrophilic, it is possible to impart a hydrophilic function higher than that of the planar surface formed by the resin to the outer surface of the porous resin. In addition, when the resin constituting the porous resin is water-repellent, the water repellency higher than that of the planar surface formed by the resin can be imparted to the outer surface of the porous resin. Therefore, by providing the surface modification liquid containing the liquid composition of the present embodiment to the object surface, a surface modification layer can be formed to easily modify the wettability of the object surface.

In addition, when the liquid composition of the present embodiment is used, the content of the polymerizable compound, the content of porogen, the irradiation conditions of the active energy ray, etc. can be appropriately adjusted to change the irregularities (irregularities derived from voids and porosity) of the porous outer surface. In addition, it is possible to improve the degree of freedom in design of the performance surface of the surface modification layer. In addition, since the liquid composition of the present embodiment can be developed by various application methods, for example, it can be applied by an inkjet method, so that the degree of freedom in design of the shape surface of the surface modification layer can be improved. Specifically, the surface modification layer can be uniformly formed not only on the flat surface but also on the curved surface.

<Use of separation layer or use of reaction layer>

When the porous resin formed of the liquid composition of the present embodiment is capable of permeating a fluid such as a liquid or a gas, the porous resin can be used as a fluid flow path. When the porous resin can be used as a flow path of the fluid, the porous resin can be used for the purpose of a separation layer separating a specified substance from the fluid or the use of a reaction layer (micro reactor) that provides a fine reaction field to the fluid. That is, it is preferable that the liquid component of this embodiment is contained in the composition for forming a separation layer or the composition for forming a reaction layer. It is preferable that the porous resin used for such applications can uniformly and efficiently permeate the fluid inside the porous resin. In this regard, since the porous resin formed by the liquid composition of the present embodiment is formed by phase separation, pores are continuously connected to provide a structure capable of uniformly and efficiently permeating fluid.

When used for separation layer use, it is preferable that the liquid composition of the present embodiment contains a polymerizable compound having a functional group capable of interacting with a predetermined substance contained in a fluid. When a porous resin is formed using such a liquid composition, functional groups capable of interacting with a predetermined material are disposed on the surfaces (inner surface and outer surface) of the porous resin to effectively separate the defined material. The polymerizable compound having a functional group capable of interacting with a predetermined substance contained in the fluid may be part of the polymerizable compound contained in the liquid composition or may be all. In addition, the functional groups capable of interacting with the substances defined herein include cases in which the functional groups themselves are capable of interacting with the substances specified by the addition of graft polymerization.

When used in a reaction layer application, it is preferable that the liquid composition of the present embodiment contains a polymerizable compound containing a functional group that provides a reaction field in a fluid. When a porous resin is formed using this liquid composition, functional groups that provide a reaction field to the fluid are placed on the surfaces of the porous resin (inner surface and outer surface) to effectively provide a reaction field. The polymerizable compound having a functional group that provides a reaction field to the fluid may be part of the polymerizable compound contained in the liquid composition, or may be all. In addition, the functional group that provides a reaction field to the fluid herein also includes a case in which the functional group itself can provide a reaction field by performing graft polymerization in addition to the case where the functional group itself can provide a reaction field.

The separation layer and the reaction layer are formed by filling and curing a liquid composition in a container capable of forming a fluid inlet and a fluid outlet, such as a glass tube. In addition, by printing the liquid composition on a substrate by an inkjet method or the like, a separation layer and a reaction layer having flow paths of a desired shape formed of a porous resin can be produced (drawn). Since the flow paths of the separation layer and the reaction layer can be printed, it is possible to provide a separation layer and a reaction layer that can appropriately change the flow path according to the purpose.

In addition, when the composition for forming the separation layer and the composition for forming the reaction layer of the present embodiment are used, the porosity or porosity of the porous resin can be changed by appropriately adjusting the content of the polymerizable compound, the content of porogen, and the irradiation conditions of the active energy ray. It is possible to improve the degree of freedom in design of the performance of the separation layer and the reaction layer.

[Example]

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

<Calculation of Hansen solubility parameter C and interaction radius D of the polymerizable compound>

Hansen solubility parameter C and interaction radius D of the following four polymerizable compounds were calculated in the following order.

Polymerizable compound X: tricyclodecane dimethanol diacrylate (manufactured by Daicel Orunecus Co., Ltd.)

Polymerizable compound Y: ε- caprolactone-modified tris-(2-acryloxy ethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerizable compound Z: pentaerythritol tetraacrylate (manufactured by Arke Masa)

Polymerizable compound X+Y: mixture of 50% by weight of polymerizable compound X and 50% by weight of polymerizable compound Y

-Preparation of composition for measuring transmittance-

First, the polymerizable compound for calculating the Hansen solubility parameter C and the interaction radius D and the following 21 kinds of evaluation solvents in which the Hansen solubility parameter (HSP) is known are prepared, and a polymerizable compound, each evaluation solvent and polymerization initiator are prepared. Was mixed at the ratio shown below to prepare a composition for measuring transmittance.

-Composition ratio for measuring transmittance-

Polymeric compound to obtain Hansen solubility parameter C: 28.0 wt%

Solvent for evaluation with known Hansen solubility parameter (HSP): 70.0 wt%

Polymerization initiator (Irgacure819, manufactured by BASF): 2.0 wt%

-Evaluation solvent group (21 types)-

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetra decaine, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethyl hexanol, diisobutyl ketone, benzyl alcohol, 1-bromo naphthalene

-Light transmittance measurement (compatibility evaluation)-

The prepared transmittance measurement composition was injected into a quartz cell and the light (visible light) transmittance at a wavelength of 550 nm of the transmittance measurement composition was measured while stirring at 300 rpm using a stirrer. In this example, when the light transmittance is 30% or more, it was determined that the polymerizable compound and the solvent for evaluation are in a commercial state, and when the light transmittance is less than 30%, the polymerizable compound and the solvent for evaluation are in an incompatible state. In addition, each condition regarding the measurement of light transmittance is as follows.

Quartz cell: Special micro cell with screw cap (brand name: M25-UV-2)

· Transmittance measurement device: USB4000 manufactured by Ocean Optics

· Stirring speed: 300rpm

Measurement wavelength: 550nm

Reference: Acquired by measuring the light transmittance with a wavelength of 550 nm while the inside of the quartz cell is air (transmittance: 100%)

In Table 1, the compatibility evaluation results of the polymerizable compound and the evaluation solvent are shown according to the following evaluation criteria.

(Evaluation standard)

a: Polymeric compound and evaluation solvent are compatible

b: Polymeric compound and solvent for evaluation are not compatible

-Calculation according to the Hansen melting method-

In the compatibility evaluation, the Hansen solubility parameter (HSP) of the evaluation solvent showing compatibility and the Hansen solubility parameter (HSP) of the evaluation solvent showing no compatibility were plotted on the Hansen space, respectively. The Hansen solubility parameter (HSP) of the evaluation solvent group which does not show compatibility, including the Hansen solubility parameter (HSP) of the evaluation solvent group showing compatibility according to the Hansen solubility parameter (HSP) of each evaluation solvent plotted is included. A virtual sphere (Hansen ball) that does not contain was created on the Hansen space. The center of the Hansen ball was calculated using the Hansen solubility parameter C and the Hansen ball radius as the interaction radius D.

-Calculated Hansen solubility parameter C and interaction radius D-

The calculated Hansen solubility parameter C and the interaction radius D of the polymerizable compound are as follows.

Polymerizable compound X: Hansen solubility parameter C (17.21, 8.42, 7.98), interaction radius D (11.8)

Polymerizable compound Y: Hansen solubility parameter C (18.51,9.04,4.75), interaction radius D (9.5)

Polymerizable compound Z: Hansen solubility parameter C (19.65, 19.25, 4.48), interaction radius D (19.8)

Polymerizable compound X+Y: Hansen solubility parameter C (17.71, 8.62, 8.67), interaction radius D (11.4)

<Calculation of Hansen solubility parameter A and interaction radius B of a resin formed by polymerization of a polymerizable compound>

Hansen solubility parameter A and interaction radius B were calculated for the resin formed by polymerizing the following four polymerizable compounds in the following order.

Polymerizable compound X: tricyclodecane dimethanol diacrylate (manufactured by Daicel Orunecus Co., Ltd.)

Polymerizable compound Y: ε-caprolactone modified tris-(2-acryloxy ethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Polymerizable compound Z: pentaerythritol tetraacrylate (manufactured by Arkema)

Polymerizable compound X+Y: mixture of 50% by weight of polymerizable compound X and 50% by weight of polymerizable compound Y

-Preparation of composition for measuring haze-

First, 21 kinds of evaluation solvents in which the precursor (polymerizable compound) and the Hansen solubility parameter (HSP) of the resin to calculate the Hansen solubility parameter A and the interaction radius B are known are prepared, and the polymerizable compound and each evaluation A composition for haze measurement was prepared by mixing the solvent and the polymerization initiator in the ratios shown below.

-Composition ratio for haze measurement-

Precursor (polymerizable compound) of the resin for which the Hansen solubility parameter A is obtained: 28.0 wt%

Solvent for evaluation with known Hansen solubility parameter (HSP): 70.0 wt%

Polymerization initiator (Irgacure819, manufactured by BASF): 2.0 wt%

-Evaluation solvent group (21 types)-

Ethanol, 2-propanol, mesitylene, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether, propylene carbonate, ethyl acetate, tetrahydrofuran, acetone, n-tetra decaine, ethylene glycol, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, 2-ethyl hexanol, diisobutyl ketone, benzyl alcohol, 1-bromo naphthalene

-Fabrication of haze measurement elements-

The resin fine particles were uniformly dispersed on the substrate by spin coating on an alkali-free glass substrate to obtain a gap agent. Subsequently, the substrate coated with the gap agent was bonded to each other by facing the alkali-free glass substrate without the gap agent. Next, the liquid composition prepared using the capillary phenomenon was filled between the bonded substrates to produce a haze measurement device before UV irradiation. Then, the composition for haze measurement was cured by UV irradiation on the haze measurement device before UV irradiation. Finally, a device for haze measurement was manufactured by sealing the periphery of the substrate with a sealing agent. The conditions at the time of production are as follows.

Alkali-free glass substrate: made by Nippon Electric Glass Co., Ltd., 40mm, t = 0.7mm, OA-10G

Gap agent: Sekisui Chemical Co., Ltd., resin fine particle micro pearl GS-L100, average particle diameter 100μm

Spin coating condition: 150 μL of dispersion dripping amount, rotation speed of 1000 rpm, rotation time of 30 s

Filled liquid composition: 160 μL

UV irradiation conditions: Use UV-LED as the light source, light source wavelength 365nm, irradiation intensity 30mW/cm ² , irradiation time 20s

Sealant: TB3035B (Three Bond company)

-Haze value (turbidity) measurement (compatibility evaluation)-

The haze value (turbidity) was measured using the haze measurement device and the haze measurement device before UV irradiation. The rise rate of the measured value of the haze measurement element before the UV irradiation was calculated by using the measured value of the haze measurement element before UV irradiation as a reference (haze value 0). In this example, when the haze value increase rate is 1.0% or more, it was determined that the resin and the solvent for evaluation are in a commercial state when the resin and the solvent for evaluation are less than 1.0%. In addition, the apparatus used for measurement is as follows.

Haze measurement device: Haze meter NDH5000 manufactured by Nippon Densoku Industries Co., Ltd., Japan

Table 2 shows the evaluation results of compatibility between the resin formed by polymerization of the polymerizable compound and the solvent for evaluation according to the following evaluation criteria.

(Evaluation standard)

a: The resin formed by polymerization of the polymerizable compound and the solvent for evaluation are not compatible

b: The resin formed by polymerization of the polymerizable compound and the solvent for evaluation are compatible.

-Calculation according to the Hansen melting method-

In the haze value (turbidity) measurement (compatibility evaluation), the Hansen solubility parameter (HSP) of the evaluation solvent showing compatibility and the Hansen solubility parameter (HSP) of the evaluation solvent showing no compatibility were plotted on the Hansen space, respectively. . The Hansen solubility parameter (HSP) of the evaluation solvent group, which does not show compatibility, includes the Hansen solubility parameter (HSP) of the evaluation solvent group which shows compatibility according to the Hansen solubility parameter (HSP) of each evaluation solvent plotted. A virtual sphere (Hansen ball) that is not included was created in the Hansen space. The center of the Hansen ball was calculated using the Hansen solubility parameter A and the Hansen ball radius as the interaction radius B.

-Calculated Hansen solubility parameter A and interaction radius B-

The Hansen solubility parameter A and the interaction radius B of the resin formed by polymerization of the calculated polymerizable compound are as follows.

Resin formed by polymerization of polymerizable compound X: Hansen solubility parameter A (20.02, 5.22, 6.15), radius of interaction B (8.3)

Resin formed by polymerization of polymerizable compound Y: Hansen solubility parameter A (19.89, 10.47, 7.32), interaction radius B (8.2)

Resin formed by polymerization of polymerizable compound Z: Hansen solubility parameter A (21.59, 7.83, 7.75), radius of interaction B (11.4)

Resin formed by polymerization of polymerizable compound X+Y: Hansen solubility parameter A (19.67, 9.68, 7.49), radius of interaction B (7.7)

<Examples 1-1>

A liquid composition was prepared by mixing the materials in the following proportions.

Polymerizable compound X: 28.0 wt%

Porogen (ethanol): 70.0 wt%

Polymerization initiator (Irgacure819 (manufactured by BASF)): 2.0 wt%

From the calculated Hansen solubility parameter C of the polymerizable compound X and the calculated radius of interaction D of the polymerizable compound X and the Hansen solubility parameter of the solvent (porogen), the relative energy difference (RED) calculated according to the following Equation 2 is 0.998. Was.

[Equation 2]

In addition, the calculated Hansen solubility parameter A of the resin formed by polymerization of the polymerizable compound X and the calculated interaction radius B of the resin formed by polymerization of the polymerizable compound X and the Hansen solubility parameter of the solvent (porogen) are as follows. The relative energy difference (RED) calculated according to Equation 1 was 1.941.

[Equation 1]

Further, the viscosity of the liquid composition at 25°C was measured using a viscometer (device name: RE-550L, manufactured by Touki-Sangyou Co., Ltd.), and was 30.0 mPa·s or less.

<Various Examples, Comparative Examples>

Liquid compositions of various examples and comparative examples were obtained in the same manner as in the preparations of Examples 1 to 1 except that the compositions of Examples 1 to 1 were changed to the compositions of Tables 3 to 10. The unit of each number in the composition of Tables 3-10 is “% by weight”. In addition, in Tables 3-10, the relative energy difference (RED) calculated according to Equation 2 (represented as "RED of polymerizable compound and porogen" in Tables 3-10) and the relative energy difference calculated according to Equation 1 ( RED) (in Tables 3-10, "Resin and Porogen RED").

In addition, the viscosity at 25 degreeC of the liquid composition of each Example and a comparative example is shown in Tables 3-10 according to the following evaluation criteria. In addition, in the evaluation of the [light transmittance] described later, when the light transmittance is less than 30% (evaluation "b"), that is, when it is determined that the components of the liquid composition are not commercially available, viscosity measurement is not performed. , In Tables 3-10, "-" is indicated.

(Evaluation standard)

a: The viscosity of the liquid composition is 30.0 mPa·s or less

b: The viscosity of the liquid composition is greater than 30.0 mPa·s

In addition, in Table 3-10, “EC/DMC/EMC mixture + LiPF ₆ ”is a mixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (weight ratio “EC:DMC:EMC = 2: For a mixture of 2:1”), LiPF ₆ as an electrolyte was added to a concentration of 1 mol/L. In addition, in Tables 3-10, for convenience, a solution containing LiPF ₆ is described in the “solvent (porogen)” column, but electrolytes such as LiPF ₆ are not defined as components included in the solvent (porogen) herein. It is defined as a component that may be included in the liquid composition.

Next, evaluation of the light transmittance of the liquid composition, evaluation of the haze change rate, evaluation of the pore size measurement, evaluation of the porosity of the resin, and evaluation of discharge stability were performed.

[Light transmittance]

Light transmittance was measured as follows using the liquid compositions of each of the adjusted Examples and Comparative Examples.

The prepared liquid composition was injected into a quartz cell, and the light (visible light) transmittance of a wavelength of 550 nm was measured while stirring at 300 rpm using a stirrer. In this embodiment, when the light transmittance is 30% or more, it was determined that the polymerizable compound and porogen are in a commercial state, and when the light transmittance is less than 30%, the polymerizable compound and porogen are in an incompatible state. In addition, the conditions regarding the measurement of the light transmittance are as follows.

Quartz cell: Special micro cell with screw-over cap (brand name: M25-UV-2)

· Transmittance measurement device: USB4000 manufactured by Ocean Optics

· Stirring speed: 300rpm

Measurement wavelength: 550nm

Reference: Acquired by measuring the light transmittance of wavelength 550nm while the inside of the quartz cell is air (transmittance: 100%)

The results of the light transmittance are shown in Tables 11-14 according to the following evaluation criteria.

(Evaluation standard)

a: Light transmittance of 30% or more

b: Light transmittance is less than 30%

[Haze change rate]

Using the liquid compositions of each of the adjusted Examples and Comparative Examples, a device for measuring haze was prepared as follows and the haze value (turbidity) was measured.

-Fabrication of haze measurement elements-

The resin fine particles were uniformly dispersed on the substrate by spin coating on an alkali-free glass substrate to obtain a gap agent. Subsequently, the substrate coated with the gap agent was bonded to each other by facing the alkali-free glass substrate without the gap agent. Next, the liquid composition prepared using the capillary phenomenon was filled between the bonded substrates to produce a haze measurement device before UV irradiation. Then, the composition for haze measurement was cured by UV irradiation on the haze measurement device before UV irradiation. Finally, a “haze measurement device” was produced by sealing the periphery of the substrate with a sealing agent. The conditions at the time of production are as follows.

Alkali-free glass substrate: made by Nippon Electric Glass Co., Ltd., 40mm, t = 0.7mm, OA-10G

Gap agent: Sekisui Chemical Company (SEKISUI CHEMICAL CO.,LTD.), resin fine particles micro pearl GS-L100, average particle diameter 100μm

Spin coating condition: 150 μL of dispersion dripping amount, rotation speed of 1000 rpm, rotation time of 30 s

Filled liquid composition: 160 μL

UV irradiation conditions: Use UV-LED as the light source, light source wavelength 365nm, irradiation intensity 30mW/cm ² , irradiation time 20s

Sealant: TB3035B (Three Bond company)

-Haze value (turbidity) measurement-

The haze value (turbidity) was measured using the haze measurement device and the haze measurement device before UV irradiation. The measured value of the haze measurement element before UV irradiation was referred to (haze value 0), and the rate of increase of the measured value of the haze measurement element (haze value) with respect to the measured value of the haze measurement element before UV irradiation was calculated. In this example, it was determined that the resin and porogen are in a non-commercial state when the haze value increase rate is 1.0% or more, and the resin and porogen are in a commercial state when the haze value is less than 1.0%. In addition, the apparatus used for measurement is as follows.

Haze measurement device: Haze meter NDH5000 manufactured by Nippon Densoku Industries Co., Ltd., Japan

The results of the haze value increase rate are shown in Tables 11-14 according to the following evaluation criteria. In addition, in the evaluation of the light transmittance, the liquid composition in which the composition of the liquid composition was judged to be incompatible was not evaluated and Tables 11-14 are denoted by “-”.

(Evaluation standard)

a: Haze value increase rate is 1.0% or more

b: Haze value increase rate is less than 1.0%

[Measurement of pore size]

Using a dispenser (manufactured by Musashi Engineering, a micro quantitative dispenser NANO MASTER SMP-II), 20 μL of the liquid composition of each Example and Comparative Example was applied to a copper foil having a thickness of 8 μm as a substrate, and then irradiated with UV under an N 2 atmosphere to obtain a polymerizable compound. Polymerized. The solvent was then removed by heating at 100° C. for 1 minute using a hot plate to form a resin. UV irradiation conditions are as follows.

·Light source: UV-LED (Phoseon company, product name: FJ800)

·Light source wavelength: 365nm

Irradiation intensity: 30mW/cm ²

Irradiation time: 20s

· UV irradiation light measuring device: manufactured by Ushio Electric Corporation, UV-integrated photometer UIT-250

Next, the surface of the produced resin was observed by SEM. As a result, except for the liquid composition in which the components of the liquid composition were judged to be incompatible in the above light transmittance evaluation (the evaluation of “light transmittance” in Tables 11 to 14 is “b”), all liquid compositions had a pore size of 0.01 μm or more. It was confirmed that a resin having pores of 10 μm or less was formed. Moreover, the resin provided with the pores formed had a common continuous structure in which a number of pores in the resin were continuously connected. In addition, in the evaluation of the above light transmittance, the liquid composition in which the components in the liquid composition were judged to be incompatible (the evaluation of “light transmittance” in Tables 11 to 14 is “b”) had pores of 0.01 μm or more and 10 μm or less. No resin was formed.

[Resin porosity]

Resin was formed using the liquid composition of each of Examples and Comparative Examples in the same manner as in the above-mentioned pore size measurement evaluation.

Next, the prepared resin was filled with unsaturated fatty acids (commercial butter), and after osmium dyeing, the cross-sectional structure inside the FIB was cut and the porosity in the resin was measured using SEM. The results of the resin porosity are shown in Tables 11-14 according to the following evaluation criteria. In addition, evaluation was not performed on the produced resin not being a porous resin, and in Tables 11-14, "-" is indicated.

(Evaluation standard)

a: Porosity of 50% or more

b: Porosity is 30% or more and less than 50%

c: Porosity is less than 30%

[Discharge stability]

The liquid composition of each Example and Comparative Example was continuously discharged for 60 minutes using an ink jet ejecting device equipped with a GEN 5 head (manufactured by Ricoh Printing Systems Co., Ltd.) for 60 minutes to obtain the number of nozzles with missing nozzles, and according to the following evaluation criteria, Stability”. The inkjet ejecting apparatus optimally adjusted the driving frequency and heating temperature for each ink, and also set the ink ejection amount per time to 2 pL. Further, the missing nozzle means that ink droplets are not ejected from the nozzle where clogging has occurred. The results of the discharge stability are shown in Tables 11-14 according to the following evaluation criteria. In addition, in the evaluation of the light transmittance described above, the liquid composition in which the components of the liquid composition are judged to be incompatible is not evaluated, and is indicated by “-” in Tables 11-14.

(Evaluation standard)

a: Nozzle missing is less than 5

b: There is a nozzle that can be discharged, but the missing nozzle is 5 or more

c: No nozzle discharge

From the results of Tables 11-14, the Hansen solubility parameter C of the polymerizable compound and the interaction radius D of the polymerizable compound, the Hansen solubility parameter of the solvent (porogen), and the relative energy difference calculated according to Equation 2 above (RED ) Is 1.05 or less, it can be seen that the compatibility of the polymerizable compound and the solvent (porogen) is high. Also, the relative energy difference (RED) calculated according to Equation 1 above is 1.00 from the Hansen solubility parameter A of the resin formed by polymerization of the polymerizable compound and the interaction radius B of the resin and the Hansen solubility parameter of the solvent (porogen). In the above case, it can be seen that the compatibility between the resin and the solvent (porogen) formed by polymerization of the polymerizable compound is low.

This selects a suitable combination of a polymerizable compound and a solvent (porogen), and the polymerizable compound and a solvent (porogen) change from a commercial state to an incompatible state according to a polymerization reaction due to UV irradiation, thereby causing phase separation, thereby causing a porous resin. Indicates that is formed. Specifically, upon UV irradiation, it is thought that the polymerizable compound causes a polymerization reaction to gradually form a resin, and in this process, the solubility of the growing resin in the solvent (porogen) decreases, resulting in phase separation. As a result, the resin is separated from the solution, and finally, the resin forms a network structure having a porous structure in which a solvent (porogen) is filled with pores. It is thought that the haze value increased accordingly. In addition, by drying the network structure, porogen is removed to obtain a porous resin having a high porosity.

In addition, the above was true not only when one type of polymerizable compound was used, but also when several types of polymerizable compounds were mixed and used.

Further, in the present embodiment, a non-dispersion-based composition that does not contain a dispersion in a liquid composition may be a dispersion-based composition containing a dispersion in a liquid composition, but it is preferably a non-dispersion-based composition as in the present embodiment. This is because, if the liquid composition is a non-dispersive composition, the liquid composition can be used for various liquid composition application means. For example, it is preferable because it is possible to stably use the inkjet method in which it is important to maintain ejection stability.

In addition, it was confirmed that all of the porous resins formed using the liquid composition of the examples are white, and the liquid composition can be preferably used as a white ink. In addition, it was confirmed that all of the liquid components of the examples are excellent in ejection stability by an inkjet ejecting apparatus and can be suitably used as white ink ejected by an inkjet method.

[Description of codes]

1a: printing device

1b: accommodation container

1c: Supply tube

2a: Light irradiation device

2b: polymerization inert gas circulation device

3a: heating device

4: printing equipment

5: Transfer section

6: Porous resin precursor

7: liquid composition

10: printing process department

20: polymerization step

30: heating process part

100: porous resin manufacturing apparatus

Claims (20)

In the liquid composition comprising a polymerizable compound and a solvent,
The liquid composition forms a porous resin,
The liquid composition has a light transmittance of 30% or more at a wavelength of 550 nm measured while stirring the liquid composition,
A liquid composition having a haze value increase rate of a haze measurement device produced using the liquid composition of 1.0% or more. According to claim 1,
The relative energy difference calculated according to Equation 1 below from the Hansen solubility parameter A of the resin formed by polymerization of the polymerizable compound, the interaction radius B of the resin, and the Hansen solubility parameter of the solvent is 1.00 or more.
[Equation 1]

According to claim 1,
The relative energy difference calculated according to Equation 2 below from the Hansen solubility parameter C of the polymerizable compound, the interaction radius D of the polymerizable compound, and the Hansen solubility parameter of the solvent is 1.05 or less.
[Equation 2]

According to claim 1,
The polymerizable compound is contained in an amount of 10.0% by weight or more and 50.0% by weight or less with respect to the liquid composition,
The solvent is a liquid composition containing 50.0% by weight or more and 90.0% by weight or less with respect to the liquid composition. According to claim 1,
A liquid composition having a viscosity at 25°C of 1 mPa·s or more and 150 mPa·s or less. According to claim 1,
A liquid composition having a viscosity at 25°C of 1 mPa·s or more and 30 mPa·s or less. According to claim 1,
The polymerizable compound is a liquid composition having a (meth)acryloyl group or a vinyl group. According to claim 1,
The porous resin is a liquid composition having a pore having a pore diameter of 0.01 μm or more and 10 μm or less. According to claim 1,
The porous resin is a liquid composition having a porosity of 30% or more. According to claim 1,
The porous resin is a liquid composition having a common continuous structure in which a plurality of pores are continuously connected. According to claim 1,
A liquid composition further containing an electrolyte. According to claim 1,
The solvent is a liquid composition comprising at least one selected from propylene carbonate, ethyl methyl carbonate, dimethyl carbonate and ethylene carbonate. A porous resin manufacturing apparatus comprising an accommodating container in which the liquid composition according to claim 1 is accommodated, an imparting means for imparting the liquid composition accommodated in the accommodating container, and a curing means for curing the imparted liquid composition. The method of claim 13,
The imparting means is a porous resin manufacturing apparatus that is a means for imparting the liquid composition to the active material layer. The method of claim 13,
The imparting means is a porous resin manufacturing apparatus which is a means for discharging the liquid composition by an inkjet method. A method for producing a porous resin comprising an imparting step of imparting the liquid composition according to claim 1 and a curing step of curing the imparted liquid composition. The method of claim 16,
The imparting step is a method of manufacturing a porous resin, which is a step of imparting the liquid composition to an active material layer formed on an electrode gas. The method of claim 16,
The imparting step is a method of manufacturing a porous resin which is a step of discharging the liquid composition by an inkjet method. A receiving container containing a liquid composition forming a porous resin having a porosity of 30% or more,
Dispensing means for discharging the liquid composition accommodated in the receiving container,
It has a curing means for curing the discharged liquid composition,
The liquid composition contains a polymerizable compound and a solvent,
A porous resin manufacturing apparatus having a viscosity at 25°C of the liquid composition of 1 mPa·s or more and 30 mPa·s or less. A discharging process for discharging a liquid composition forming a porous resin having a porosity of 30% or more,
It has a curing process for curing the discharged liquid composition,
The liquid composition contains a polymerizable compound and a solvent,
A method for producing a porous resin having a viscosity at 25°C of the liquid composition of 1 mPa·s or more and 30 mPa·s or less.

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